Synthesis and characterization of poly(vinyl acetate peroxide)

Poly(vinyl acetate peroxide) (PVACP) was prepared from vinyl acetate by free-radical-initiated oxidative polymerization. The polyperoxide was isolated and characterized by different spectroscopic methods. The extreme instability of PVACP was demonstrated by FTIR spectroscopy. The H-1- and C-13-NMR studies show the irregularities in the polyperoxide chain due to the cleavage reactions of the propagating peroxide radical. Thermal degradation studies using differential scanning calorimetry revealed that PVACP degrades at a lower temperature and the heat of degradation is in the same range as reported for other vinyl polyperoxides. (C) 1996 John Wiley & Sons, Inc.

Zn(II), Cd(II) and Hg(II) complexes with 1-(p-methoxybenzyl)-2-(p-methoxyphenyl)benzimidazole: Syntheses, structures and luminescence

Five coordination compounds Zn(mbmpbi)(2)Cl-2 (1), Zn(mbmpbi)(2)Br-2 (2), Cd(mbmpbi)(2)Cl-2 (3), Hg(mbmpbi)(2)Cl-2 (4) and Hg(mbmpbi)(2)Br-2 (5) were synthesized by the reaction of 1-(p-methoxybenzyl)-2-(p-methoxyphenyl)benzimidazole (mbmpbi) with the corresponding metal halides. The complexes have been characterized by elemental analysis, conductance measurements, FT-IR, H-1 NMR and photoluminescence spectral studies. The ligand mbmpbi exhibits the N-benzimidazole coordination. The structures of 3-5 have been determined by single crystal X-ray diffraction. These three complexes are isostructural, crystallizing in the monoclinic system. P2/n space group with a distorted tetrahedral geometry around the metal ion. Zn(II) and Cd(II) complexes show strong blue emission in solid state at room temperature. (C) 2011 Elsevier Ltd. All rights reserved.

Synthesis, structural characterization, thermal studies and chain dynamics of poly(methacrylonitrile peroxide) by NMR spectroscopy

Poly(methacrylonitrile peroxide) (PMNP) has been synthesized from methacrylonitrile by free radical initiated oxidative polymerization and characterized by different spectroscopic methods. NMR spectroscopy confirmed the alternating copolymer structure with labile peroxy bonds in the main chain. The extreme instability of PMNP was noted from FTIR spectroscopy. Thermal degradation studies by using differential scanning calorimetry and thermogravimetry have revealed that PMNP degrades highly exothermically and the heat of degradation, 42.5 kcal mol−1, is of the same order as that reported for other vinyl polyperoxides. Mass spectral fragmentation pattern under electron impact (EI) condition has also been investigated. The mechanism of the primary exothermic degradation has been substantiated by thermochemical calculations. The chain dynamics of the polyperoxide chain has been studied by means of 13C spin–lattice relaxation times (T1) of the main chain as well as the side chain carbons. The temperature dependence of the spin–lattice relaxation times shows that the PMNP is more flexible compared to the analogous poly(styrene peroxide).

Carrier density-dependent transport in poly(3-methylthiophene): from injection-limited to space-charge-limited current

Current-voltage (I-V) and impedance measurements were carried out in doped poly(3-methylthiophene) devices by varying the carrier density. As the carrier concentration reduces the I-V characteristics indicate that the conduction mechanism is limited by metal-polymer interface, as also observed in impedance data. The temperature dependence of I-V in moderately doped samples shows a trap-controlled space-charge-limited conduction (SCLC); whereas in lightly doped devices injection-limited conduction is observed at lower bias and SCLC at higher voltages. The carrier density-dependent quasi-Fermi level adjustment and trap-limited transport could explain this variation in conduction mechanism. Capacitance measurements at lower frequencies and higher bias voltages show a sign change in values due to the significant variations in the relaxation behaviour for lightly and moderately doped samples. The electrical hysteresis increases as carrier density is reduced due to the time scales involved in the de-trapping of carriers.

Thermally induced phase separation in P alpha MSAN/PMMA blends in presence of functionalized multiwall carbon nanotubes: Rheology, morphology and electrical conductivity

The focus of this work is the evaluation and analysis of the state of dispersion of functionalized multiwall carbon nanotubes (CNTs), within different morphologies formed, in a model LCST blend (poly[(alpha-methylstyrene)-co-(acrylonitrile)]/poly(methyl-methacryla te), P alpha MSAN/PMMA). Blend compositions that are expected to yield droplet-matrix (85/15 P alpha MSAN/PMMA and 15/85 P alpha MSAN/PMMA, wt/wt) and co-continuous morphologies (60/40 P alpha MSAN/PMMA, wt/wt) upon phase separation have been combined with two types of CNTs; carboxylic acid functionalized (CNTCOOH) and polyethylene modified (CNTPE) up to 2 wt%. Thermally induced phase separation in the blends has been studied in-situ by rheology and dielectric (conductivity) spectroscopy in terms of morphological evolution and CNT percolation. The state of dispersion of CNTs has been evaluated by transmission electron microscopy. The experimental results indicate that the final blend morphology and the surface functionalization of CNT are the main factors that govern percolation. In presence of either of the CNTs, 60/40 P alpha MSAN/PMMA blends yield a droplet-matrix morphology rather than co-continuous and do not show any percolation. On the other hand, both 85/15 P alpha MSAN/PMMA and 15/85 P alpha MSAN/PMMA blends containing CNTPEs show percolation in the rheological and electrical properties. Interestingly, the conductivity spectroscopy measurements demonstrate that the 15/85 P alpha MSAN/PMMA blends with CNTPEs that show insulating properties at room temperature for the miscible blends reveal highly conducting properties in the phase separated blends (melt state) as a result of phase separation. By quenching this morphology, the conductivity can be retained in the blends even in the solid state. (C) 2011 Elsevier Ltd. All rights reserved.

Synthesis, Characterization, and Degradation of Biodegradable Poly(mannitol citric dicarboxylate) Copolyesters

Three groups of poly(mannitol citric dicarboxylate) [p(MCD)] copolyesters were synthesized by catalyst-free melt condensation of mannitol with acids. The resulting copolyesters were designated as poly(mannitol citric succinate) [p(MCSu)], poly(mannitol citric adipate) [p(MCA)], poly(mannitol citric sebacate) [p(MCS)]. The polymers were characterized by FTIR, (1)H NMR, and DSC analysis. The synthesized p(MCD) polymers exhibit glass transition temperatures ranging from 16.5 to 58.58 degrees C. The mechanical, degradation properties, and the drug-releasing characteristics of these polymers were investigated. It was observed that the mechanical properties of the p(MCD) polymers cover a wide range with Young's modulus of the polymer varying from 12.25 to 660 MPa. Hydrolytic degradation of all polymers was investigated by incubating polymer discs in PBS and the hydrolytic degradation of p(MCD) polymers followed the order, p(MCSu) > p(MCA) > p(MCS). This was attributed to the number of -CH(2)(units in the dicarboxylic monomers. The release of model drug compounds from the p(MCD) polymer discs was also studied. POLYM. ENG. SCI., 51:2035-2043, 2011. (C) 2011 Society of Plastics Engineers

Anisotropic electrical transport properties of poly(methyl methacrylate) infiltrated aligned carbon nanotube mats

We report the electrical anisotropic transport properties of poly(methyl methacrylate) infiltrated aligned carbon nanotube mats. The anisotropy in the resistivity increases with decreasing temperature and the conduction mechanism in the parallel and perpendicular direction is different. Magnetoresistance (MR) studies also suggest anisotropic behavior of the infiltrated mats. Though MR is negative, an upturn is observed when the magnetic field is increased. This is due to the interplay of electron weak localization and electron-electron interactions mechanisms. Overall, infiltrated carbon nanotube mat is a good candidate for anisotropically conductive polymer composite and a simple fabrication method has been reported. (C) 2012 American Institute of Physics. [doi: 10.1063/1.3675873]

Surface chemical and adsorption studies using Thiobacillus ferrooxidans with reference to bacterial adhesion to sulfide minerals

Adhesion of Thiobacillus ferrooxidans to pyrite and chalcopyrite in relation to its importance in bioleaching and bioflotation has been studied. Electrokinetic studies as well as FT-IR spectra suggest that the surface chemistry of Thiobacillus ferrooxidans depends on bacterial growth conditions. Sulfur-,Pyrite- and chalcopyrite-grown Thiobacillus ferrooxidans were found to be relatively more hydrophobic. The altered surface chemistry of Thiobacillus ferrooxidans was due to secretion of newer and specific proteinaceous compounds. The adsorption density corresponds to a monolayer coverage in a horizontal orientation of the cells. The xanthate flotation of pyrite in presence of Thiobacillus ferrooxidans is strongly depressed where as the cells have insignificant effect on chalcopyrite flotation. This study demonstrate that: (a)Thiobacillus ferrooxidans cells can be used for selective flotation of chalcopyrite from pyrite and importantly at natural pH values. (b)Sulfur-grown cells exhibits higher leaching kinetics than ferrous ion-grown cells.

Study of molecular structure and vibrational spectra of poly (beta,-1-malic acid) PMLA] using DFT approach

Poly (beta-L-malic acid) (PMLA) is a biodegradable polymer and it has various important applications in the biomedical field. In the present work the structural and spectral characteristics of PMLA have been studied by methods of infrared. Raman spectroscopy and quantum chemistry. Electrostatic potential surface, optimized geometry, harmonic vibrational frequencies, infrared intensities and activities of Raman scattering were calculated by density functional theory (DFT) using oligomeric approach employing B3LYP with complete relaxation in the potential energy surface using 6-311++G (d, p) basis set. Based on results, we have discussed the correlation between the vibrational modes and the structure of the PMLA. A complete analysis of the experimental infrared and Raman spectra has been reported on the basis of wavenumber of the vibrational bands and potential energy distribution. The calculated HOMO and LUMO energies shows that charge transfer occur within the molecule. The calculated infrared and the Raman spectra of the polymer based on DFT calculations show reasonable agreement with the experimental results. (c) 2012 Elsevier Ltd. All rights reserved.

Size dependent structural relaxations and dielectric properties induced by surface functionalized MWNTs in poly(vinylidene fluoride)/poly(methyl methacrylate) blends

Structural dynamics, dielectric permittivity and ferroelectric properties in poly(vinylidene fluoride) (PVDF)/poly(methyl methacrylate) (PMMA) (PVDF/PMMA) blends with respect to crystalline morphology was systematically investigated in presence of amine functionalized MWNTs (NH2-MWNTs) using dielectric spectroscopy. The crystalline morphology and the crystallization driven demixing in the blends was assessed by light microscopy (LM), wide angle X-ray diffraction (WXRD) and, in situ, by shear rheology. The crystal nucleation activity of PVDF was greatly induced by NH2-MWNTs, which also showed two distinct structural relaxations in dielectric loss owing to mobility confinement of PVDF chains and smaller cooperative lengths. The presence of crystal-amorphous interphase was supported by the presence of interfacial polarization at lower frequencies in the dielectric loss spectra. On contrary, the control blends showed a single broad relaxation at higher frequency due to defective crystal nuclei. This was further supported by monitoring the dielectric relaxations during isothermal crystallization of PVDF in the blends. These observations were addressed with respect to the spherulite sizes which were observed to be larger in case of blends with NH2-MWNTs. Higher dielectric permittivity with minimal losses was also observed in blends with NH2-MWNTs as compared to neat PVDF. Polarization obtained using P-E (polarization-electric field) hysteresis loops was higher in case of blends with NH2-MWNTs in contrast to control blends and PVDF. These observations were corroborated with the charge trapped at the crystal-amorphous interphase and larger crystal sizes in the blends with NH2-MWNTs. The microstructure and localization of MWNTs were assessed using SEM.

Structural, thermal and electrical properties of poly(methyl methacrylate)/CaCu3Ti4O12 composite sheets fabricated via melt mixing

Poly(methyl methacrylate) (PMMA) and CaCu3Ti4O12 (CCTO) composites were fabricated via melt mixing followed by hot pressing technique. These were characterized using X-ray diffraction, thermo gravimetric, thermo mechanical, differential scanning calorimetry, fourier transform infrared (FTIR) and Impedance analyser for their structural, thermal and dielectric properties. Composites were found to have better thermal stability than that of pure PMMA. However, there was no significant difference in the glass transition (T (g) ) temperature between the polymer and the composite. The appearance of additional vibrational frequencies in the range 400-600 cm(-1) in FTIR spectra indicated a possible interaction between PMMA and CCTO. The composite, with 38 vol% of CCTO (in PMMA), exhibited remarkably low dielectric loss at high frequencies and the low-frequency relaxation is attributed to the interfacial polarization/MWS effect. The origin of AC conductivity particularly in the high-frequency region was attributed to the electronic polarization.

Fabrication and characterization of poly(methyl methacrylate)/CaCu3Ti4O12 composites

Composites comprising Poly(Methyl Methacrylate) (PMMA) and CaCu3Ti4O12 (CCTO) via melt mixing followed by hot pressing were fabricated. These were characterized using X-ray diffraction, thermo gravimetric, scanning electron microscopy, and Impedance analyzer for their structural, morphology, and dielectric properties. Composites were found to have better thermal stability than that of pure PMMA. The composite, with 38 Vol % of CCTO (in PMMA), exhibited remarkably low dielectric loss at high frequencies and the low frequency relaxation is attributed to the space charge polarization/MWS effect. Theoretical models were employed to rationalize the dielectric behavior of these composites. At higher temperatures, the relaxation peak shifts to higher frequencies, due to the merging of both beta and alpha relaxations into a single dielectric dispersion peak. The AC conductivity in the high frequency region was attributed to the electronic polarization. POLYM. ENG. SCI., 54:551-558, 2014. (c) 2013 Society of Plastics Engineers

New single-source precursor for bismuth sulfide and its use as low-cost counter electrode material for dye-sensitized solar cells

One new homoleptic Bi(dtc)(3)] (1) (dtc = 4-hydroxypiperdine dithiocarbamate) has been synthesized and characterized by microanalysis, IR, UV-Vis, H-1 and C-13 spectroscopy and X-ray crystallography. The photoluminescence spectrum for the compound in DMSO solution was recorded. The crystal structure of 1 displayed distorted octahedral geometry around the Bi(III) center bonded through sulfur atoms of the dithiocarbamate ligands. TGA indicates that the compound decomposes to a Bi and Bi-S phase system. The Bi and Bi-S obtained from decomposition of the compound have been characterized by pXRD, EDAX and SEM. Solvothermal decomposition of 1 in the absence and presence of two different capping agents yielded three morphologically different Bi2S3 systems which were deployed as counter-electrode in dye-sensitized solar cells (DSSCs). (C) 2015 Elsevier B.V. All rights reserved.

NMR relaxation studies in doped poly-3-methylthiophene

NMR relaxation rates (1/T-1), magnetic susceptibility, and electrical conductivity studies in doped poly-3-methylthiophene are reported in this paper. The magnetic susceptibility data show the contributions from both Pauli and Curie spins, with the size of the Pauli term depending strongly on the doping level. Proton and fluorine NMR relaxation rates have been studied as a function of temperature (3-300 K) and field (for protons at 0.9, 9.0, 16.4, and 23.4 T, and for fluorine at 9.0 T). The temperature dependence of T-1 is classified into three regimes: (a) For T < (g mu(B) B/2k(B)), the relaxation mechanism follows a modified Korringa relation due to electron-electron interactions and disorder. H-1-T-1 is due to the electron-nuclear dipolar interaction in addition to the contact term. (b) For the intermediate temperature range (g mu(B) B/2k(B)) < T < T-BPP (the temperature where the contribution from the reorientation motion to the T-1 is insignificant) the relaxation mechanism is via spin diffusion to the paramagnetic centers. (c) In the high-temperature regime and at low Larmor frequency the relaxation follows the modified Bloembergen, Purcell, and Pound model. T-1 data analysis has been carried out in light of these models depending upon the temperature and frequency range of study. Fluorine relaxation data have been analyzed and attributed to the PF6 reorientation. The cross relaxation among the H-1 and F-19 nuclei has been observed in the entire temperature range suggesting the role of magnetic dipolar interaction modulated by the reorientation of the symmetric molecular subgroups. The data analysis shows that the enhancement in the Korringa ratio is greater in a less conducting sample. Intra-and interchain hopping of charge carriers is found to be a dominant relaxation mechanism at low temperature. Frequency dependence of T-1(-1) on temperature shows that at low temperature T < (g mu(B) B/2k(B))] the system shows three dimensions and changes to quasi one dimension at high temperature. Moreover, a good correlation between electrical conductivity, magnetic susceptibility, and NMR T-1 data has been observed.